6,7-Methylenedioxy-isochromane arthropodicide synergizing agents

ABSTRACT

6,7-Methylenedioxy-isochromanes of the formula ##STR1## in which R, R 1  and R 2  each independently is hydrogen or alkyl, which synergize with known arthropodicides.

The present invention relates to and has for its objects the provisionof particular new 6,7-methylenedioxyisochromanes which synergize withknown compounds of known arthropodicidal activity, active composition inthe form of synergistic mixtures of such compounds optionally with solidand liquid dispersible carrier vehicles, and methods for producing suchcompounds and for using such compounds in a new way especially forcombating pests, e.g. insects, and acarids, with other and furtherobjects becoming apparent from a study of the within specification andaccompanying examples.

The invention relates to certain new isochromane derivatives, to aprocess for their preparation and to their use as synergistic agents inarthropodicidal, especially insecticidal and acaricidal, compositions.

It is already known that the following active compounds or groups ofactive compounds possess pesticidal, especially insecticidal andacaricidal, properties:

(A) carbamates, for example 2-iso-propoxy-phenyl N-methylcarbamate,3,4,5-trimethyl-phenyl N-methyl-carbamate, 1-naphthylN-methyl-carbamate, 2,3-dihydro-2,2-dimethyl-7-benzofuranylN-methyl-carbamate, 2-(1,3-dioxolan-2-yl-phenyl) N-methyl-carbamate and2,2-dimethyl-1,3-benzodioxol-4-yl N-methyl carbamate,

(B) carboxylic acid esters, for example2,3,4,5-tetra-hydro-phthalimido-methyl chrysanthemate and(5-benzyl-3-furyl)-methyl2,2-dimethyl-3-(2-methyl-propenyl)-cyclo-propane-carboxylate,

(C) phosphoric acid esters, for exampleO,O-dimethyl-O-(2,2-dichlorovinyl)-phosphoric acid ester and

(D) halogenoalkanes, for example1,1,1-trichloro-2,2-bis-(4-methoxyphenyl)-ethane and1,1,1-trichloro-2,2-bis-(4-chlorophenyl)-ethane.

In addition, synergistic mixtures of carbamates, for example2-iso-propoxy-phenyl N-methylcarbamate, or of phosphoric acid esters,for exampleO,O-diethyl-O-(2-iso-propyl-4-methylpyrimidin-6-yl)-thionophosphoricacid ester, or of natural or synthetic pyrethroids, with piperonylethers, for exampleα-(2-(2-butoxy-ethoxy)-ethoxy)-4,5-methylenedioxy-2-propyl-toluene, areknown (see Bull. Org. mond. Sante/Bull. Wld.Hlth Org. 1966, 35 691-708;and Schrader, G., Die Entwicklung neuer insektizider Phosphorsaureester(The Development of New Insecticidal Phosphoric Acid Esters), 1963, page158). However, the activity of these synergistic active compoundcombinations is not satisfactory. Hitherto, onlyα-(2-(2-butoxy-ethoxy)-ethoxy)-4,5-methylenedioxy-2-propyl-toluene hasattained some practical importance.

The present invention now provides, as new compounds, the isochromanederivatives of the general formula ##STR2## in which R, R¹ and R²,independently of one another, each represent hydrogen or alkyl.

Preferably, R, R¹ and R², independently of one another, each representhydrogen or straight-chain or branched alkyl with 1 to 5 (especially 1to 3) carbon atoms.

The invention also provides a process for the preparation of anisochromane derivative of the formula (I) in which a benzodioxolederivative of the general formula ##STR3## in which R and R¹ have theabove-mentioned meanings, is reacted with an aldehyde of the generalformula ##STR4## in which R² has the above-mentioned meaning, ifappropriate in the presence of a catalyst and, if appropriate, in thepresence of a diluent.

The invention also provides an arthropodicidal composition containing asactive ingredients (1) at least one isochromane derivative of theformula (I) and (2) at least one compound selected from (A) carbamates,(B) carboxylic acid esters (including the natural and syntheticpyrethrods), (C) phosphoric acid esters and (D) halogenoalkanes, aloneor in admixture with a diluent or carrier.

The invention also provides a method of combating arthropods, especiallyinsects or acarids, which comprises applying to the arthropods, or to ahabitat thereof, a composition according to this invention.

The synergistic action of the compounds of the general formula (I)manifests itself preferentially with compounds of certain preferredclasses.

Preferred carbamates (A) are those of the general formula ##STR5## inwhich R¹ represents aryl, a heterocyclic ring or an oxime radical,

R² represents hydrogen or an alkyl radical with 1 to 4 carbon atoms and

R³ represents alkyl, alkylcarbonyl with 1 to 6 carbon atoms in the alkylradical, which optionally can also be substituted by hydroxyl ormethylthio, or the radical --S--Z,

wherein

Z represents an optionally halogen-substituted aliphatic radical with 1to 4 carbon atoms (especially CCl₃ and CF₃), an optionally substitutedaryl radical (especially phenyl) (preferred substituents being nitrile,halogen, especially chlorine, methyl, trihalogenomethyl,trifluoromethylmercapto or nitro), methoxycarbonyl or the radical##STR6## wherein W represents alkyl, halogenoalkyl, alkylamino,dialkylamino or an optionally substituted aryl radical (preferredsubstituents being halogen, trihalogenomethyl, nitrile, methyl ornitro).

Particularly preferred carbamates of the formula (II) are those wherein

R¹ represents phenyl or naphthyl, which are optionally substituted byalkyl, alkenyl, alkoxy, alkylmercapto or alkylthioalkyl, in each casewith 1 to 6 carbon atoms, dialkylamino and dialkenylamino, with up to 3carbon atoms per alkyl or alkenyl part, halogen, especially chlorine,dioxolanyl or the --N═CH--N(C₁₋₄ -alkyl)₂ radical, or

wherein

R¹ represents 2,3-dihydrobenzofuranyl, benzodioxole, benzothienyl,pyrimidinyl or pyrazolyl, which are optionally substituted by alkyl with1 to 4 carbon atoms (especially methyl) and/or dialkylamino with 1 to 4carbon atoms per alkyl part, or

wherein

R¹ represents a radical of the general formula ##STR7## in which R⁴ andR⁵, which may be identical or different, each represent alkyl,cycloalkyl, alkenyl, alkynyl, alkoxy, alkylmercapto, alkoxycarbonyl,amidocarbonyl, or alkylmercaptoalkyl, in each case with up to 5 carbonatoms, nitrile, aryl (especially phenyl), or R⁴ and R⁵ conjointlyrepresent a dioxolanyl or dithiolanyl radical which is optionallysubstituted by C₁₋₄ -alkyl.

The following carbamates of the formula (II) may be mentionedspecifically: 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl,2-methoxyphenyl, 2-ethoxyphenyl, 2-isopropoxyphenyl, 4-methylphenyl,4-ethylphenyl, 4-n-propylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl,4-n-propoxyphenyl, 3,4,5-trimethylphenyl, 1-naphthyl,2,3-dihydro-2,2-dimethyl-7-benzofuranyl, 2-(1,3-dioxolan-2-yl-phenyl)and 2,2-dimethyl-1,3-benzodioxol-4-yl N-methyl-carbamate and thecorresponding N-methyl-N-acetyl-, N-methyl-N-trifluoromethylthio-,N-methyl-N-dichloromonofluoromethylthio- andN-methyl-N-dimethylaminothio-carbamates.

Preferred carboxylic acid esters (B) are those of the general formula##STR8## in which R⁶ represents alkyl, aralkyl, aryl or cycloalkyl, anyof which can optionally be substituted,

R⁷ represents hydrogen, alkyl, halogenoalkyl, alkenyl, alkynyl ornitrile and

R⁸ represents aryl or a heterocylic ring, or conjointly with R⁷ forms anoptionally substituted cyclopentenone ring.

Particularly preferred carboxylic acid esters of the formula (III) arethose in which

R⁶ represents alkyl with 1 to 6 carbon atoms, which is optionallysubstituted by optionally halogen-substituted phenyl, or representscyclopropyl, which is optionally substituted by alkyl, alkenyl,halogenoalkyl or halogenoalkenyl, each with up to 6 carbon atoms, orrepresents phenyl, which is optionally substituted by halogen,

R⁷ represents hydrogen, alkyl with 1 to 6 carbon atoms, halogenoalkylwith 1 to 4 carbon atoms and up to 3 halogen atoms, nitrile or ethynyl,

R⁸ represents phenyl which is optionally substituted by C₁₋₄ -alkyl,halogen, especially fluorine or chlorine, or optionallyhalogen-substituted or methyl-substituted phenoxy or optionallysubstituted benzyl, or represents furanyl, tetrahydrophthalimido, orbenzodioxole, which are optionally substituted by halogen, especiallyfluorine, alkyl or alkenyl with up to 4 carbon atoms, or benzyl, ortogether with R⁷ and the CH moiety represents cyclopentenone, which isoptionally substituted by C₁₋₄ -alkyl, furfuryl or C₁₋₅ -alkenyl.

The following may be mentioned specifically:1-(3,4-dichlorophenyl)-2,2,2-trichloroethyl acetate,2,3,4,5-tetrahydrophthalimidomethyl chrysanthemate and(5-benzyl-3-furyl)methyl2,2-dimethyl-3-(2-methyl-propenyl)-cyclopropanecarboxylate. In addition,the naturally occurring pyrethroids are also particularly preferred.

Preferred phosphoric acid esters (C) are those of the general formula##STR9## in which each X' independently of the others represents O or S,

Y' represents O, S, --NH-- or a direct bond between the central P atomand R¹¹, and

R⁹ and R¹⁰, which may be identical or different, each represent alkyl oraryl, and

R¹¹ represents alkyl, aryl, heteroaryl, aralkyl, alkenyl, dioxanyl or anoxime radical or a radical identical to that to which it is bonded.

Particularly preferred phosphoric acid esters (IV) are those in which

R⁹ and R¹⁰, which may be identical or different, each represent C₁₋₄-alkyl or phenyl, and

R¹¹ represents alkyl with 1 to 4 carbon atoms, which is optionallysubstituted by halogen, hydroxyl, nitrile, optionallyhalogen-substituted phenyl, amidocarbonyl, C₁₋₄ -alkylamidocarbonyl,sulphonyl-C₁₋₄ -alkyl, sulphoxy-C₁₋₄ -alkyl, carbonyl-C₁₋₄ -alkyl, C₁₋₄-alkoxy, C₁₋₄ -alkylmercapto or C₁₋₄ -alkoxy-carbonyl, or representsalkenyl with up to 4 carbon atoms, which is optionally substituted byhalogen, optionally halogen-substituted phenyl or alkoxy-carbonyl, orrepresents an oxime radical of the general formula ##STR10## wherein R⁴and R⁵ have the above-mentioned meanings, but preferably represent cyanoor phenyl, or R¹¹ represents dioxanyl which is substituted by a radicalidentical to that to which R¹¹ is bonded, or R¹¹ represents a radicalidentical to that to which it is bonded, or R¹¹ represents phenyl whichis optionally substituted by methyl, nitro, nitrile, halogen ormethylthio, or, particularly preferentially , R¹¹ represents anoptionally C₁₋₄ -alkyl-substituted or halogen-substitutedhetero-aromatic, such as pyridine, quinoline, quinoxaline, pyrimidine,diazinone or benzo-1,2,4-triazine.

The following may be mentioned specifically: O,O-dimethyl- andO,O-diethyl-O-(2,2-dichloro- or 2,2-dibromo-vinyl)phosphoric acid ester,O,O-diethyl-O-(4-nitro-phenyl)thionophosphoric acid ester,O,O-dimethyl-O-(3-methyl-4-methylthio)-thionophosphoric acid ester,O,O-dimethyl-O-(3-methyl-4-nitro)-thionophosphoric acid ester,O-ethyl-S-n-propyl-O-(2,4-dichlorophenyl)-thionophosphoric acid ester,O-ethyl-S-n-propyl-O-(4-methylthio-phenyl)-thionophosphoric acid ester,O,O-dimethyl-S-(4-oxo-1,2,3-benzotriazin-3-yl-methyl)-thionothiolphosphoricacid ester,O-methyl-O-(2-iso-propyl-6-methoxy-pyrimidin-4-yl)-thionomethanephosphonicacid ester,O,O-diethyl-O-(2-iso-propyl-6-methyl-pyrimidin-4-yl)-thionophosphoricacid ester,O,O-diethyl-O-(3-chloro-4-methyl-coumarin-7-yl)-thionophosphoric acidester, O,O-dimethyl-2,2,2-trichloro-hydroxy-ethane-phosphonic acid esterand O,O-dimethyl-S-(methylcarbamoylmethyl)-thionophosphoric acid ester.

Preferred halogenoalkanes (D) are those of the general formula ##STR11##in which Hal' represents chlorine or bromine and

R¹² represents hydrogen or hydroxyl,

R¹³ and R¹⁴, which may be identical or different, each representhalogen, alkyl or alkoxy and

R¹⁵ represents hydrogen or halogen.

Particularly preferred halogenoalkanes (V) are those in which

R¹² represents hydrogen or hydroxyl,

R¹³ and R¹⁴ are identical and represent halogen, alkyl with 1 to 4carbon atoms or alkoxy with 1 to 4 carbon atoms and

R¹⁵ represents halogen.

The following may be mentioned specifically:1,1,1-trichloro-2,2-bis(4-chloro- or 4-methoxy-phenyl)-ethane,1,1,1-trichloro-2-hydroxy-2,2-bis(4-chlorophenyl)-ethane and1,1-dichloro-2,2-bis(4-ethylphenyl)-ethane.

Surprisingly, the insecticidal and/or acaricidal action of the activecompound combinations according to the invention is substantiallygreater than the action of the individual components and greater thanthe sum of the actions of the individual components. Furthermore, it issubstantially greater than the action of the previously known activecompound combination of 2-iso-propoxy-phenyl N-methyl-carbamate andpiperonyl butoxide. In addition, the isochromane derivatives which canbe used according to the invention exhibit an excellent synergisticactivity, not only with one class of active compounds, but with activecompounds from a great variety of groups of chemical compounds.

Accordingly, the isochromane derivatives according to the invention, andthe synergistic mixtures containing these derivatives, represent avaluable enrichment of the art.

The following may be mentioned as examples of the compounds of theformula (I): 6,7-methylenedioxy-isochromane, 1-methyl-, 1-ethyl-,1-n-propyl-, 1-iso-propyl-, 3-methyl-, 3-ethyl-, 3-n-propyl-,3-iso-propyl-, 4-methyl-, 4-ethyl-, 4-n-propyl-, 4-iso-propyl-,1,3-dimethyl-, 1,3-diethyl-, 1,3-di-n-propyl-, 1,3-di-iso-propyl-,1,4-dimethyl-, 1,4-diethyl-, 1,4-di-n-propyl-, 1,4-di-iso-propyl-,3,4-dimethyl-, 3,4-diethyl-, 3,4-di-n-propyl-, 1-methyl-3-ethyl-,1-methyl-3-n-propyl-, 1-methyl-3-iso-propyl-, 1-methyl-4-ethyl-,1-methyl-4-n-propyl-, 1-methyl-4-iso-propyl-, 3-methyl-4-ethyl-,3-methyl-4-n-propyl-, 3-methyl-4-iso-propyl-, 1-ethyl-3-methyl-,1-ethyl-3-n-propyl-, 1-ethyl-3-iso-propyl-, 1-ethyl-4-methyl-,1-ethyl-4-n-propyl-, 1-ethyl-4-iso-propyl-, 3-ethyl-4-methyl-,3-ethyl-4-n-propyl-, 3-ethyl-4-iso-propyl-, 1-n-propyl-3-methyl-,1-n-propyl-3-ethyl-, 1-n-propyl-3-iso-propyl-, 1-n-propyl-4-methyl-, 1-n-propyl-4-ethyl-, 1-n-propyl-4-iso-propyl-, 3-n-propyl-4-methyl-,3-n-propyl-4-ethyl-, 3-n-propyl-4-iso-propyl-, 1-iso-propyl-3-methyl-,1-iso-propyl-3-ethyl-, 1-iso-propyl-3-n-propyl-, 1-iso-propyl-4-methyl-,1-iso-propyl-4-ethyl-, 1-iso-propyl-4-n-propyl-, 3-iso-propyl-4-methyl-,3-iso-propyl-4-ethyl-, 3-iso-propyl-4-n-propyl-, 1,3,4-trimethyl-,1,3,4-triethyl-, 1,3,4-tri-n-propyl-, 1-ethyl-3,4-dimethyl-,1-n-propyl-3,4-dimethyl-, 1-iso-propyl-3,4-dimethyl-,1-methyl-3,4-diethyl-, 1-n-propyl-3,4-diethyl-,1-iso-propyl-3,4-di-n-propyl-, 1-sio-propyl-3,4-diethyl-,1-methyl-3,4-di-n-propyl-, 1-ethyl-3,4-di-n-propyl-,1,3-dimethyl-4-ethyl-, 1,3-dimethyl-4-n-propyl-,1,3-dimethyl-4-iso-propyl-, 1,3-diethyl-4-methyl-,1,3-diethyl-4-n-propyl-, 1,3-diethyl-4-iso-propyl-,1,3-di-n-propyl-4-methyl-, 1,3-di-n-propyl-4-ethyl-,1,3-di-n-propyl-4-iso-propyl-, 1,3-di-iso-propyl-4-methyl-,1,3-di-iso-propyl-4-ethyl-, 1,3-di-iso-propyl-4-n-propyl-,1,4-dimethyl-3-ethyl-, 1,4-dimethyl-3-n-propyl-,1,4-dimethyl-3-iso-propyl-, 1,4-diethy- 3-methyl-,1,4-diethy-3-n-propyl-, 1,4-diethyl-3-iso-propyl-,1,4-di-n-propyl-3-methyl-, 1,4-di-n-propyl-3-ethyl-,1,4-di-n-propyl-3-iso-propyl-, 1,4-di-iso-propyl-3-methyl-,1,4-di-iso-propyl-3-ethyl-, 1,4-di-iso-propyl-3-n-propyl-,3,4-dimethyl-1-ethyl-, 3,4-di-methyl-1-n-propyl-,3,4-dimethyl-1-iso-propyl-, 3,4-diethyl-1-methyl-,3,4-diethyl-1-n-propyl-, 3,4-diethyl-1-iso-propyl-,3,4-di-n-propyl-1-methyl-, 3,4-di-n-propyl-1-ethyl-,1-methyl-3-ethyl-4-n-propyl-, 1-methyl-3-ethyl-4-iso-propyl-,1-methyl-3-n-propyl-4-ethyl-, 1-methyl-3-n-propyl-4-iso-propyl-,1-methyl-3-iso-propyl-4-ethyl-, 1-methyl-3-iso-propyl-4-n-propyl-,1-ethyl-3-methyl-4-n-propyl-, 1-ethyl-3-methyl-4-iso-propyl-,1-ethyl-3-n-propyl-4-methyl-, 1-ethyl-3-n-propyl-4-iso-propyl-,1-ethyl-3-iso-propyl-4-methyl-, 1-ethyl-3-iso-propyl-4-n-propyl-,1-n-propyl-3-methyl-4-iso-propyl-, 1-n-propyl-3-methyl-4-ethyl-,1-n-propyl-3-ethyl-4-iso-propyl-, 1-n-propyl-3-ethyl-4-methyl-,1-n-propyl-3-iso-propyl-4-methyl-, 1-n-propyl-3-iso-propyl-4-ethyl-,1-iso-propyl-3-methyl-4-ethyl-, 1-iso-propyl-3-methyl-4-n-propyl-,1-iso-propyl-3-ethyl-4-methyl-, 1-iso-propyl-3-ethyl-4-n-propyl-,1-iso-propyl-3-n-propyl- 4-methyl- and1-iso-propyl-3-n-propyl-4-ethyl-6,7-methylenedioxy-isochromane.

The benzodioxole derivatives to be used as starting materials aredefined by the formula (Ia). The following may be mentioned as examples:4-(2-hydroxy-ethyl)-, 4-(2-hydroxy-n-propyl)-, 4-(2-hydroxy-n-butyl)-,4-(2-hydroxy-n-pentyl)-, 4-(2-hydroxy-iso-pentyl)-,4-(1-methyl-2-hydroxyethyl)-, 4-(1-ethyl-2-hydroxy-ethyl)-,4-(1-n-propyl-2-hydroxy-ethyl)-, 4-(1-iso-propyl-2-hydroxy-ethyl)-,4-(1-methyl-2-hydroxy-n-propyl)-, 4-(1-ethyl-2-hydroxy-n-propyl)-,4-(1-n-propyl-2-hydroxy-n-propyl)-,4-(1-iso-propyl-2-hydroxy-n-propyl)-, 4-(1-methyl-2-hydroxy-n-butyl)-,4-(1-ethyl-2-hydroxy-n-butyl)-, 4-(1-n-propyl-2-hydroxy-n-butyl)-,4-(1-iso-propyl-2-hydroxy-n-butyl)-, 4-(1-methyl-2-hydroxy-n-pentyl)-,4-(1-ethyl-2-hydroxy-n-pentyl)-, 4-(1-n-propyl-2-hydroxy-n-pentyl)-,4-(1-iso-propyl-2-hydroxy-n-pentyl)-,4-(1-methyl-2-hydroxy-iso-pentyl)-, 4-(1-ethyl-2-hydroxy-iso-pentyl)-and 4-(1-n-propyl-2-hydroxy-iso-pentyl)-1,2-methylenedioxy-benzene.

Benzodioxole derivatives of the formula (Ia) are known (see DT-OS(German Published Specification) No. 2,624,693). They can be preparedif, for example, known compounds of the formula ##STR12## wherein R hasthe above-mentioned meaning and

Z represents COR¹, COOR¹, or CN, with R¹ having the above-mentionedmeaning,

are reduced in accordance with known methods. (See Ber. Deutsch. Chem.Ges. 41 (1908) pages 2,751-2,761).

In a special case (R=H; R¹ =CH₃), isosafrol is used as the startingmaterial and oxidized to the epoxide which is subjected to thermal orcatalytic rearrangement (Hoering, Ber. Dt. Chem. Ges. 38, 2296-99; idem.3464-3488 (1905)), and the resulting piperonyl methyl ketone is reducedto the corresponding alcohol. ##STR13##

The aldehydes of the formula (Ib) also to be used as starting materialare known. The following may be mentioned as examples: formaldehyde,acetaldehyde, propionaldehyde, butyraldehyde and isobutyraldehyde.

The process for the preparation of the compounds according to theinvention is optionally carried out using a suitable diluent. Virtuallyany inert organic solvent can be used for this purpose, especiallyaliphatic and aromatic, optionally chlorinated hydrocarbons such asbenzene, chlorobenzene, dichlorobenzene, toluene, xylene, methylenechloride, ethylene chloride, chloroform and carbon tetrachloride.

The process according to the invention is in general carried out usingan acidic catalyst. Preferably, (gaseous) hydrogen chloride is used forthis purpose.

The reaction temperature can be varied within a substantial range. Ingeneral, the reaction is carried out at about 0° to 80° C., preferablyat about 10° to 50° C. The reaction is in general carried out undernormal pressure.

In carrying out the process according to the invention, about 1.0 to1.5, preferably about 1.1 to 1.3, mols of aldehyde of the formula (Ib)are in general employed per mol of hydroxy-alkylbenzodioxole derivativeof the formula (Ia). In general, the components are introduced into oneof the stated diluents and are stirred for several hours at the statedtemperatures, while passing hydrogen chloride through the mixture.Working up is effected by washing with water, drying the organic phaseand stripping off the solvent in vacuo. The crude products thus obtainedcan be purified by vacuum distillation or recrystallization. They arecharacterized by the melting point.

As already mentioned, combinations of the isochromane derivativesaccording to the invention with carbamates, carboxylic acid esters,phosphoric acid esters and halogenoalkanes exhibit an outstandingincrease in action compared to the individual active compounds andcompared to the sum of their actions.

The weight ratios of the groups of active compounds can vary withinrelatively wide ranges. In general, the isochromane component (1) isemployed together with the remaining active compounds in component (2)in a ratio of about 0.1:10 to 10:0.1. However, ratios, in the mixture,of about 0.5:1.0 to 3.0:1.0 have proved particularly suitable.

The active compound combinations are well tolerated by plants, have afavorable level of toxicity to warm-blooded animals, and can be used forcombating arthropod pests, especially insects and acarids, which areencountered in agriculture, in forestry, in the protection of storedproducts and of materials, and in the hygiene field. They are activeagainst normally sensitive and resistant species and against all or somestages of development. The abovementioned pests include:

from the class of the Isopoda, for example Oniscus asellus,Armadillidium vulgare and Porcellio scaber;

from the class of the Dipolopoda, for example Blaniulus guttulatus;

from the class of the Chilopoda, for example Geophilus carpophagus andScutigera spec.;

from the class of the Symphyla, for example Scutigerella immaculata;

from the order of the Thysanura, for example Lepisma saccharina;

from the order of the Collembola, for example Onychiurus armatus;

from the order of the Orthoptera, for example Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratorioides,Melanoplus differentialis and Schistocerca gregaria;

from the order of the Dermaptera, for example Forficula auricularia;

from the order of the Isoptera, for example Reticultiermes spp.;

from the order of the Anoplura, for example Phylloxera vastatrix,Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. andLinognathus spp.;

from the order of the Mallophaga, for example Trichodectes spp. andDamalinea spp.;

from the order of the Thysanoptera, for example Hercinothrips femoralisand Thrips tabaci;

from the order of the Heteroptera, for example Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.;

from the order of the Homoptera, for example Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosomalanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp..,Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus,Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphaxstriatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotushederae, Pseudococcus spp. and Psylla spp.;

from the order of the Lepidoptera, for example Pectinophora gossypiella,Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella,Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria,Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella,Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Eariasinsulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolisflammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsapomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestiakeuhniella, Galleria mellonella, Cacoecia podana, Capua reticulana,Choristoneura fumiferana, Clysia ambiguella, Homona magnanima andTortrix viridana;

from the order of the Coleoptera, for example Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestia, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus holoeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphilmallon solstitialis and Costelytra zealandica;

from the order of the Hymenoptera, for example Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.;

from the order of the Diptera, for example Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebgra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa;

from the order of the Siphonaptera, for example Xenopsylla cheopis andCeratophyllus spp.;

from the class of the Arachnida, for example Scorpio maurus andLatrodectus mactans;

from the order of the Acarina, for example Acarus siro, Argas spp.,Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptrutaoleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommaspp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusting agents, foams, pastes, soluble powders, granules, aerosols,suspension-emulsion concentrates, seed-treatment powders, natural andsynthetic materials impregnated with active compound, very fine capsulesin polymeric substances, coating compositions for use on seed, andformulations used with burning equipment, such as fumigating cartridges,fumigating cans and fumigating coils, as well as ULV cold mist and warmmist formulations.

These formulations may be produced in known manner, for example bymixing the active compounds with extenders, that is to say liquid orliquefied gaseous or solid diluents or carriers, optionally with the useof surface-active agents, that is to say emulsifying agents and/ordispersing agents and/or foam-forming agents. In the case of the use ofwater as an extender, organic solvents can, for example, also be used asauxiliary solvents.

As liquid diluents or carriers, especially solvents, there are suitablein the main, aromatic hydrocarbons, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane orparaffins, for example mineral oil fractions, alcohols, such as butanolor glycol as well as their ethers and esters, ketones, such as acetone,methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, orstrongly polar solvents, such as dimethylformamide anddimethylsulphoxide, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which wouldbe gaseous at normal temperature and under normal pressure, for exampleaerosol propellants, such as halogenated hydrocarbons as well as butane,propane, nitrogen and carbon dioxide.

As solid carriers there may be used ground natural minerals, such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals, such ashighly-dispersed silicic acid, alumina and silicates. As solid carriersfor granules there may be used crushed and fractionated natural rockssuch as calcite, marble, pumice, sepiolite and dolomite, as well assynthetic granules of inorganic and organic meals, and granules oforganic material such as sawdust, coconut shells, corn cobs and tobaccostalks.

As emulsifying and/or foam-forming agents there may be used non-ionicand anionic emulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products. Dispersing agents include, for example,lignin suphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, can be used in theformulations.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs or metal phthalocyaninedyestuffs, and trace nutrients, such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain from 0.1 to 95 percent by weight ofactive compound, preferably from 0.5 to 90 percent by weight.

The active compounds according to the invention may be used in the formof their formulations of the types that are commercially available or inthe use forms prepared from these formulations.

The active compound content of the use forms prepared from theformulations of the types that are commercially available can varywithin wide ranges. The active compound concentration of the use formscan be from 0.0000001 to 100% by weight of active compound, preferablyfrom 0.01 to 10% by weight.

The compounds may be employed in a customary manner appropriate for theparticular use forms.

When used against pests harmful to health and pests of stored products,the active compounds are distinguished by an excellent residual activityon wood and clay as well as a good stability to alkali on limedsubstrates.

Furthermore, the invention provides crops protected from damage byarthropods by being grown in areas in which immediately prior to and/orduring the time of the growing a composition of the present inventionwas applied.

It will be seen that the usual methods of providing a harvested crop maybe improved by the present invention.

PREPARATIVE EXAMPLES Example 1: ##STR14##

Hydrogen chloride was passed into a mixture of 57 g (0.34 mol) of4-(2-hydroxy-ethyl)-1,2-methylenedioxybenzene, 12.8 g (0.45 mol) offormaldehyde and 200 ml of ethylene chloride, while cooling at 20° C.,until a clear solution had formed. The solution was stirred for 6 hoursat 40° C. while passing hydrogen chloride through it, and was thenstirred overnight at room temperature, washed with water and sodiumbicarbonate solution and dried. After stripping off the solvent invacuo, the crude product which remained was purified by vacuumdistillation. Yield 38 g (63% of theory), boiling point 122° C./3 mm Hg.The product crystallized after trituration with ether/petroleum ether;melting point 87° C.

Example 2 ##STR15##

Hydrogen chloride was passed into a mixture of 90 g (0.5 mol) of4-(2-hydroxy-n-propyl)-1,2-methylenedioxybenzene, 18.8 g (0.625 mol) offormaldehyde and 250 ml of ethylene chloride at 15° to 20° C., until aclear solution had formed. The solution was stirred for 6 hours at 40°to 45° C., left to stand overnight, poured into ice-water, washed withwater and sodium bicarbonate solution and dried. The solvent wasdistilled in vacuo and the crude product was purified by vacuumdistillation.

Yield 41 g (43% of theory), boiling point 136° C./3 mm Hg. The productcrystallized after trituration with ether/petroleum ether; melting point73° C.

The activity of the compounds of this invention is illustrated by thefollowing example:

Example 3 LT₁₀₀ test

Test insects: Musca domestica, Weymanns strain (resistant to carbamatesand phosphoric acid esters)

Solvent: Acetone

Solutions were prepared from the active compounds, synergistic agentsand mixtures of active compounds and synergistic agents, and 2.5 ml ofthe solutions were pipetted onto filter paper discs of 9.5 cm diameterin Petri dishes. The filter paper adsorbed the solutions. The Petridishes were left standing open until the solvent had completelyevaporated. 25 test insects were then introduced into the Petri dishes,and the dishes were covered with a glass lid.

The condition of the test insects was checked continuously for up to 6hours. The time required for a 100% knock-down action was determined. Ifthe LT₁₀₀ was not reached after 6 hours, the percentage of the testanimal which had been knocked down was determined.

In this test, the compounds of Examples 1 and 2 exhibited a superioraction compared with the prior art.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What we claim is:
 1. An arthropodicidal composition containing as activeingredients an anthropodicidally effective amount of (1) at least onecompound of the formula ##STR16## in which R, R¹ and R² eachindependently is hydrogen or alkyl, and (2) at least one compoundselected from the group consisting of (A) carbamates, (B) carboxylicacid esters, (C) phosphoric acid esters and (D) halogenoalkanes.
 2. Acomposition according to claim 1, wherein the weight ratio of component(1) to component (2) is from about 0.1:10 to 10:0.1.
 3. A method ofcombating arthropods which comprises applying to the arthropods, or to ahabitat thereof, an arthropodicidally effective amount of a compositionaccording to claim
 1. 4. The method according to claim 3 whereincomponent (A) is6,7-methylenedioxy-isochromane or3-methyl-6,7-methylenedioxy-isochromane.